Pentafluoropropane compositions

ABSTRACT

The present invention relates to compositions of pentafluoropropane and a fluorinated propane having from 1 to 5 fluorine atoms; a hydrocarbon having from 1 to 5 carbon atoms; 1,1,1,4,4,4-hexafluorobutane, (CF 3 ) 2  CHCH 3 , dimethyl ether; or 1,1,1,2,3,4,4,5,5,5-decafluoropentane. The compositions, which may be azeotropic or azeotrope-like, may be used as refrigerants, cleaning agents, expansion agents for polyolefins and polyurethanes, aerosol propellants, refrigerants, heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents or displacement drying agents.

FIELD OF THE INVENTION

This invention relates to compositions that include pentafluoropropane.These compositions are useful as cleaning agents, expansion agents forpolyolefins and polyurethanes, aerosol propellants, refrigerants, heattransfer media, gaseous dielectrics, fire extinguishing agents, powercycle working fluids, polymerization media, particulate removal fluids,carrier fluids, buffing abrasive agents, and displacement drying agents.

BACKGROUND OF THE INVENTION

Fluorinated hydrocarbons have many uses, one of which is as arefrigerant. Such refrigerants include dichlorodifluoromethane (CFC-12)and chlorodifluoromethane (HCFC-22).

In recent years it has been pointed out that certain kinds offluorinated hydrocarbon refrigerants released into the atmosphere mayadversely affect the stratospheric ozone layer. Although thisproposition has not yet been completely established, there is a movementtoward the control of the use and the production of certainchlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) under aninternational agreement.

Accordingly, there is a demand for the development of refrigerants thathave a lower ozone depletion potential than existing refrigerants whilestill achieving an acceptable performance in refrigeration applications.Hydrofluorocarbons (HFCs) have been suggested as replacements for CFCsand HCFCs since HFCs have no chlorine and therefore have zero ozonedepletion potential.

In refrigeration applications, a refrigerant is often lost duringoperation through leaks in shaft seals, hose connections, solderedjoints and broken lines. In addition, the refrigerant may be released tothe atmosphere during maintenance procedures on refrigeration equipment.If the refrigerant is not a pure component or an azeotropic orazeotrope-like composition, the refrigerant composition may change whenleaked or discharged to the atmosphere from the refrigeration equipment,which may cause the refrigerant to become flammable or to have poorrefrigeration performance.

Accordingly, it is desirable to use as a refrigerant a singlefluorinated hydrocarbon or an azeotropic or azeotrope-like compositionthat includes one or more fluorinated hydrocarbons.

Fluorinated hydrocarbons may also be used as a cleaning agent or solventto clean, for example, electronic circuit boards. It is desirable thatthe cleaning agents be azeotropic or azeotrope-like because in vapordegreasing operations the cleaning agent is generally redistilled andreused for final rinse cleaning.

Azeotropic or azeotrope-like compositions that include a fluorinatedhydrocarbon are also useful as blowing agents in the manufacture ofclosed-cell polyurethane, phenolic and thermoplastic foams, aspropellants in aerosols, as heat transfer media, gaseous dielectrics,fire extinguishing agents, power cycle working fluids such as for heatpumps, inert media for polymerization reactions, fluids for removingparticulates from metal surfaces, as carrier fluids that may be used,for example, to place a fine film of lubricant on metal parts, asbuffing abrasive agents to remove buffing abrasive compounds frompolished surfaces such as metal, as displacement drying agents forremoving water, such as from jewelry or metal parts, as resistdevelopers in conventional circuit manufacturing techniques includingchlorine-type developing agents, or as strippers for photoresists whenused with, for example, a chlorohydrocarbon such as1,1,1-trichloroethane or trichloroethylene.

SUMMARY OF THE INVENTION

The present invention relates to the discovery of compositions ofpentafluoropropane and a fluoropropane such as tetrafluoropropane,trifluoropropane, difluoropropane or fluoropropane;1,1,1,4,4,4-hexafluorobutane; (CF₃)₂ CHCH₃ ;1,1,1,2,3,4,4,5,5,5-decafluoropentane; a hydrocarbon such as butane,cyclopropane, isobutane, propane; or propylene; or dimethyl ether. Thesecompositions are useful as refrigerants, cleaning agents, expansionagents for polyolefins and polyurethanes, aerosol propellants, heattransfer media, gaseous dielectrics, fire extinguishing agents, powercycle working fluids, polymerization media, particulate removal fluids,carrier fluids, buffing abrasive agents, and displacement drying agents.Further, the invention relates to the discovery of binary azeotropic orazeotrope-like compositions comprising effective amounts ofpentafluoropropane and a fluoropropane such as tetrafluoropropane,trifluoropropane, difluoropropane or fluoropropane;1,1,1,4,4,4-hexafluorobutane; (CF₃)₂ CHCH₃ ;1,1,1,2,3,4,4,5,5,5-decafluoropentane; a hydrocarbon such as butane,cyclopropane, isobutane, propane or propylene; or dimethyl ether to forman azeotropic or azeotrope-like composition.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ca and HFC-245eb at 25° C.;

FIG. 2 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ca and HFC-263fb at 25° C.;

FIG. 3 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ca and HFC-272ca at 25° C.;

FIG. 4 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ca and HFC-272ea at 25° C.;

FIG. 5 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ca and HFC-356mff at 25° C.;

FIG. 6 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ca and HFC-356mmz at 25° C.;

FIG. 7 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ca and butane at 20° C.;

FIG. 8 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ca and cyclopropane at 25° C.;

FIG. 9 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ca and isobutane at 25° C.;

FIG. 10 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ca and propane at 25° C.;

FIG. 11 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245cb and HFC-245eb at 25° C.;

FIG. 12 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245cb and HFC-254ca at 25° C.;

FIG. 13 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245cb and HFC-272ea at 25° C.;

FIG. 14 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245cb and HFC-281ea at 25° C.;

FIG. 15 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245cb and HFC-281fa at 25° C.;

FIG. 16 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245cb and butane at 25° C.;

FIG. 17 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245cb and cyclopropane at 25° C.;

FIG. 18 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245cb and DME at 25° C.;

FIG. 19 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245cb and isobutane at 25° C.;

FIG. 20 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245cb and propane at 25° C.;

FIG. 21 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245cb and propylene at 25° C.;

FIG. 22 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ea and HFC-272ca at 25° C.;

FIG. 23 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ea and HFC-272ea at 25° C.;

FIG. 24 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ea and HFC-356mff at 25° C.;

FIG. 25 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ea and HFC-356mmz at 25° C.;

FIG. 26 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ea and HFC-4310mee at 25° C.;

FIG. 27 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ea and butane at 25° C.;

FIG. 28 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ea and cyclopropane at 25° C.;

FIG. 29 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ea and isobutane at 25° C.;

FIG. 30 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245ea and propane at 25° C.;

FIG. 31 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245eb and HFC-263ca at 25° C.;

FIG. 32 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245eb and HFC-263fb at 25° C.;

FIG. 33 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245eb and HFC-356mff at 25° C.;

FIG. 34 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245eb and HFC-356mmz at 25° C.;

FIG. 35 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245eb and butane at 25° C.;

FIG. 36 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245eb and cyclopropane at 25° C.;

FIG. 37 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245eb and isobutane at 25° C.;

FIG. 38 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245eb and propane at 25° C.;

FIG. 39 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245fa and HFC-263ca at 25° C.;

FIG. 40 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245fa and HFC-272ca at 25° C.;

FIG. 41 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245fa and HFC-272fb at 25° C.;

FIG. 42 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245fa and butane at 25° C.;

FIG. 43 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245fa and cyclopropane at 25° C.; and

FIG. 44 is a graph of the vapor/liquid equilibrium curve for mixtures ofHFC-245fa and isobutane at 25° C.

DETAILED DESCRIPTION

The present invention relates to compositions of pentafluoropropane anda fluorinated propane having from 1 to 5 fluorine atoms; a hydrocarbonhaving from 1 to 5 carbon atoms; 1,1,1,4,4,4-hexafluorobutane; (CF₃)₂CHCH₃ ; dimethyl ether (DME); or 1,1,1,2,3,4,4,5,5,5-decafluoropentane.

As used herein, pentafluoropropane includes 1,1,2,2,3-pentafluoropropane(HFC-245ca), 1,1,1,2,2-pentafluoropropane (HFC-245cb),1,1,2,3,3-pentafluoropropane (HFC-245ea), 1,1,1,2,3-pentafluoropropane(HFC-245eb) and 1,1,1,3,3-pentafluoropropane (HFC-245fa). As usedherein, a fluorinated propane having from 1 to 5 fluorine atoms includes1,1,1,2,3-pentafluoropropane (HFC-245eb), 1,2,2,3-tetrafluoropropane(HFC-254ca), 1,2,2-trifluoropropane (HFC-263ca), 1,1,1-trifluoropropane(HFC-263fb), 2,2-difluoropropane (HFC-272ca), 1,2-difluoropropane(HFC-272ea), 1,1-difluoropropane (HFC-272fb), 2-fluoropropane(HFC-281ea) and 1-fluoropropane (HFC-281fa). As used herein, ahydrocarbon having from 1 to 5 carbon atoms includes butane,cyclopropane, isobutane, propane and propylene.

Examples of these compositions include:

(a) HFC-245ca and HFC-245eb, HFC-263fb, HFC-272ca, HFC-272ea,1,1,1,4,4,4-hexafluorobutane (HFC-356mff), (CF₃)₂ CHCH₃ (HFC-356mmz),butane, cyclopropane, isobutane or propane;

(b) HFC-245cb and HFC-245eb, HFC-254ca, HFC-272ea, HFC-281ea, HFC-281fa,butane, cyclopropane, DME, isobutane, propane or propylene;

(c) HFC-245ea and HFC-272ca, HFC-272ea, HFC-356mff, HFC-356mmz,1,1,1,2,3,4,4,5,5,5-decafluoropentane (HFC-4310mee), butane,cyclopropane, isobutane or propane;

(d) HFC-245eb and HFC-263ca, HFC-263fb, HFC-356mff, HFC-356mmz, butane,cyclopropane, isobutane or propane; or

(e) HFC-245fa and HFC-263ca, HFC-272ca, HFC-272fb, butane, cyclopropaneor isobutane.

1-99 wt. % of each of the components of the compositions can be used asrefrigerants. Further, the present invention also relates to thediscovery of azeotropic or azeotrope-like compositions of effectiveamounts of each of the above mixtures to form an azeotropic orazeotrope-like composition.

By "azeotropic" composition is meant a constant boiling liquid admixtureof two or more substances that behaves as a single substance. One way tocharacterize an azeotropic composition is that the vapor produced bypartial evaporation or distillation of the liquid has the samecomposition as the liquid from which it was evaporated or distilled,that is, the admixture distills/refluxes without compositional change.Constant boiling compositions are characterized as azeotropic becausethey exhibit either a maximum or minimum boiling point, as compared withthat of the non-azeotropic mixtures of the same components.

By "azeotrope-like" composition is meant a constant boiling, orsubstantially constant boiling, liquid admixture of two or moresubstances that behaves as a single substance. One way to characterizean azeotrope-like composition is that the vapor produced by partialevaporation or distillation of the liquid has substantially the samecomposition as the liquid from which it was evaporated or distilled,that is, the admixture distills/refluxes without substantial compositionchange. Another way to characterize an azeotrope-like composition isthat the bubble point vapor pressure and the dew point vapor pressure ofthe composition at a particular temperature are substantially the same.

It is recognized in the art that a composition is azeotrope-like if,after 50 weight percent of the composition is removed such as byevaporation or boiling off, the difference in vapor pressure between theoriginal composition and the composition remaining after 50 weightpercent of the original composition has been removed is less than 10percent, when measured in absolute units. By absolute units, it is meantmeasurements of pressure and, for example, psia, atmospheres, bars,torr, dynes per square centimeter, millimeters of mercury, inches ofwater and other equivalent terms well known in the art. If an azeotropeis present, there is no difference in vapor pressure between theoriginal composition and the composition remaining after 50 weightpercent of the original composition has been removed.

Therefore, included in this invention are compositions of effectiveamounts of

(a) HFC-245ca and HFC-245eb, HFC-263fb, HFC-272ca, HFC-272ea,HFC-356mff, HFC-356mmz, butane, cyclopropane, isobutane or propane;

(b) HFC-245cb and HFC-245eb, HFC-254ca, HFC-272ea, HFC-281ea, HFC-281fa,butane, cyclopropane, DME, isobutane, propane or propylene;

(c) HFC-245ea and HFC-272ca, HFC-272ea, HFC-356mff, HFC-356mmz,HFC-4310mee, butane, cyclopropane, isobutane or propane;

(d) HFC-245eb and HFC-263ca, HFC-263fb, HFC-356mff, HFC-356mmz, butane,cyclopropane, isobutane or propane; or

(e) HFC-245fa and HFC-263ca, HFC-272ca, HFC-272fb, butane, cyclopropaneor isobutane;

such that after 50 weight percent of an original composition isevaporated or boiled off to produce a remaining composition, thedifference in the vapor pressure between the original composition andthe remaining composition is 10 percent or less.

For compositions that are azeotropic, there is usually some range ofcompositions around the azeotrope point that, for a maximum boilingazeotrope, have boiling points at a particular pressure higher than thepure components of the composition at that pressure and have vaporpressures at a particular temperature lower than the pure components ofthe composition at that temperature, and that, for a minimum boilingazeotrope, have boiling points at a particular pressure lower than thepure components of the composition at that pressure and have vaporpressures at a particular temperature higher than the pure components ofthe composition at that temperature. Boiling temperatures and vaporpressures above or below that of the pure components are caused byunexpected intermolecular forces between and among the molecules of thecompositions, which can be a combination of repulsive and attractiveforces such as van der Waals forces and hydrogen bonding.

The range of compositions that have a maximum or minimum boiling pointat a particular pressure, or a maximum or minimum vapor pressure at aparticular temperature, may or may not be coextensive with the range ofcompositions that have a change in vapor pressure of less than about 10%when 50 weight percent of the composition is evaporated. In those caseswhere the range of compositions that have maximum or minimum boilingtemperatures at a particular pressure, or maximum or minimum vaporpressures at a particular temperature, are broader than the range ofcompositions that have a change in vapor pressure of less than about 10%when 50 weight percent of the composition is evaporated, the unexpectedintermolecular forces are nonetheless believed important in that therefrigerant compositions having those forces that are not substantiallyconstant boiling may exhibit unexpected increases in the capacity orefficiency versus the components of the refrigerant composition.

The vapor pressure of the components at 25° C. are:

    ______________________________________                                        Components        Psia   kPa                                                  ______________________________________                                        HFC-245ca         14.2   98                                                   HFC-245cb         67.4   465                                                  HFC-245ea         8.62   59                                                   HFC-245eb         16.9   117                                                  HFC-245fa         21.4   148                                                  HFC-263fb         54.0   372                                                  HFC-272ca         34.5   238                                                  HFC-272ea         20.8   143                                                  HFC-356mff        14.7   101                                                  HFC-356mmz        16.6   114                                                  butane            35.2   243                                                  cyclopropane      105.0  724                                                  isobutane         50.5   348                                                  propane           137.8  950                                                  HFC-254ca         13.7   94                                                   HFC-28lea         47.1   325                                                  HFC-281fa         37.7   260                                                  DME               85.7   591                                                  propylene         165.9  1144                                                 HFC-4310mee       4.36   30                                                   HFC-263ca         18.2   125                                                  HFC-272fb         26.5   183                                                  ______________________________________                                    

Substantially constant boiling, azeotropic or azeotrope-likecompositions of this invention comprise the following (all compositionsare measured at 25° C.):

    ______________________________________                                                        WEIGHT                                                                        RANGES       PREFERRED                                        COMPONENTS      (wt. %/wt %) (wt. %./wt. %)                                   ______________________________________                                        HFC-245ca/HFC-245eb                                                                           1-99/1-99    30-99/1-70                                       HFC-245ca/HFC-263fb                                                                           1-36/64-99   1-36/64-99                                       HFC-245ca/HFC-272ca                                                                           1-55/45-99   1-55/45-99                                       HFC-245ca/HFC-272ea                                                                           1-99/1-99    1-99/1-99                                        HFC-245ca/HFC-356mff                                                                          1-99/1-99    1-80/20-99                                       HFC-245ca/HFC-356mmz                                                                          1-99/1-99    1-80/20-99                                       HFC-245ca/butane                                                                              1-73/27-99   20-73/27-80                                      HFC-245ca/cyclopropane                                                                        1-55/45-99   1-55/45-99                                       HFC-245ca/isobutane                                                                           1-65/35-99   1-65/35-99                                       HFC-245ca/propane                                                                             1-57/43-99   1-57/43-99                                       HFC-245cb/HFC-245eb                                                                           70-99.5/0.5-30                                                                             70-99.5/0.5-30                                   HFC-245cb/HFC-254ca                                                                           74-99/1-26   74-99/1-26                                       HFC-245cb/HFC-272ea                                                                           75-99/1-25   75-99/1-25                                       HFC-245cb/HFC-281ea                                                                           1-99/1-99    40-99/1-60                                       HFC-245cb/HFC-281fa                                                                           59-99/1-41   59-99/1-41                                       HFC-245cb/butane                                                                              59-99/1-41   59-99/1-41                                       HFC-245cb/cyclopropane                                                                        1-90/10-99   30-90/10-70                                      HFC-245cb/DME   1-89/11-99   40-89/11-60                                      HFC-245cb/isobutane                                                                           40-99/1-60   40-99/1-60                                       HFC-245cb/propane                                                                             1-76/24-99   10-76/24-90                                      HFC-245cb/propylene                                                                           1-69/31-99   10-69/31-90                                      HFC-245ea/HFC-272ca                                                                           1-45/55-99   1-45/55-99                                       HFC-245ea/HFC-272ea                                                                           1-55/45-99   1-55/45-99                                       HFC-245ea/HFC-356mff                                                                          1-54/46-99   1-54/46-99                                       HFC-245ea/HFC-356mmz                                                                          145/55-99    1-45/55-99                                       HFC-245ea/HFC-4310mee                                                                         1-56 44-99   1-56/44-99                                       HFC-245ea/butane                                                                              1-65/35-99   1-65/35-99                                       HFC-245ea/cyclopropane                                                                        1-54/46-99   1-54/46-99                                       HFC-245ea/isobutane                                                                           1-62/38-99   1-62/38-99                                       HFC-245ea/propane                                                                             1-57/43-99   1-57/43-99                                       HFC-245eb/HFC-263ca                                                                           1-99/1-99    10-99/1-90                                       HFC-245eb/HFC-263fb                                                                           1-43/57-99   1-43/57-99                                       HFC-245eb/HFC-356mff                                                                          11-99/1-89   11-99/1-89                                       HFC-245eb/HFC-356mmz                                                                          1-99/1-99    1-70/30-99                                       HFC-245eb/butane                                                                              21-71/29-79  21-71/29-79                                      HFC-245eb/cyclopropane                                                                        1-56/44-99   1-56/44-99                                       HFC-245eb/isobutane                                                                           1-66/34-99   1-66/34-99                                       HFC-245eb/propane                                                                             1-57/43-99   1-57/43-99                                       HFC-245fa/HFC-263ca                                                                           1-99/1-99    1-80/20-99                                       HFC-245fa/HFC-272ca                                                                           1-99/1-99    1-99/1-99                                        HFC-245fa/HFC-272fb                                                                           1-99/1-99    1-99/1-99                                        HFC-245fa/butane                                                                              1-78/22-99   1-78/22-99                                       HFC-245fa/cyclopropane                                                                        1-56/44-99   1-56/44-99                                       HFC-245fa/isobutane                                                                           1-70/30-99   1-70/30-99                                       ______________________________________                                    

For purposes of this invention, "effective amount" is defined as theamount of each component of the inventive compositions which, whencombined, results in the formation of an azeotropic or azeotrope-likecomposition. This definition includes the amounts of each component,which amounts may vary depending on the pressure applied to thecomposition so long as the azeotropic or azeotrope-like compositionscontinue to exist at the different pressures, but with possibledifferent boiling points.

Therefore, effective amount includes the amounts, such as may beexpressed in weight percentages, of each component of the compositionsof the instant invention which form azeotropic or azeotrope-likecompositions at temperatures or pressures other than as describedherein.

For the purposes of this discussion, azeotropic or constant-boiling isintended to mean also essentially azeotropic or essentially-constantboiling. In other words, included within the meaning of these terms arenot only the true azeotropes described above, but also othercompositions containing the same components in different proportions,which are true azeotropes at other temperatures and pressures, as wellas those equivalent compositions which are part of the same azeotropicsystem and are azeotrope-like in their properties. As is well recognizedin this art, there is a range of compositions which contain the samecomponents as the azeotrope, which will not only exhibit essentiallyequivalent properties for refrigeration and other applications, butwhich will also exhibit essentially equivalent properties to the trueazeotropic composition in terms of constant boiling characteristics ortendency not to segregate or fractionate on boiling.

It is possible to characterize, in effect, a constant boiling admixturewhich may appear under many guises, depending upon the conditionschosen, by any of several criteria:

The composition can be defined as an azeotrope of A, B, C (and D . . . )since the very term "azeotrope" is at once both definitive andlimitative, and requires that effective amounts of A, B, C (and D . . .) for this unique composition of matter which is a constant boilingcomposition.

It is well known by those skilled in the art, that, at differentpressures, the composition of a given azeotrope will vary at least tosome degree, and changes in pressure will also change, at least to somedegree, the boiling point temperature. Thus, an azeotrope of A, B, C(and D . . . ) represents a unique type of relationship but with avariable composition which depends on temperature and/or pressure.Therefore, compositional ranges, rather than fixed compositions, areoften used to define azeotropes.

The composition can be defined as a particular weight percentrelationship or mole percent relationship of A, B, C (and D . . . ),while recognizing that such specific values point out only oneparticular relationship and that in actuality, a series of suchrelationships, represented by A, B, C (and D . . . ) actually exist fora given azeotrope, varied by the influence of pressure.

An azeotrope of A, B, C (and D . . . ) can be characterized by definingthe compositions as an azeotrope characterized by a boiling point at agiven pressure, thus giving identifying characteristics without undulylimiting the scope of the invention by a specific numerical composition,which is limited by and is only as accurate as the analytical equipmentavailable.

The azeotrope or azeotrope-like compositions of the present inventioncan be prepared by any convenient method including mixing or combiningthe desired amounts. A preferred method is to weigh the desiredcomponent amounts and thereafter combine them in an appropriatecontainer.

Specific examples illustrating the invention are given below. Unlessotherwise stated therein, all percentages are by weight. It is to beunderstood that these examples are merely illustrative and in no way areto be interpreted as limiting the scope of the invention.

EXAMPLE 1 Phase Study

A phase study shows the following compositions are azeotropic, all at25° C.

    ______________________________________                                                                Vapor Press.                                          Composition No.         psia   (kPa)                                          ______________________________________                                        HFC-245ca/HFC-245eb                                                                            75.0/25.0  14.1   97                                         HFC-245ca/HFC-272ca                                                                            17.2/82.8  35.8   247                                        HFC-245ca/HFC-272ea                                                                            17.6/82.4  21.1   145                                        HFC-245ca/HFC-356mff                                                                           28.0/72.0  16.9   117                                        HFC-245ca/HFC-356mmz                                                                           21.6/78.4  18.5   128                                        HFC-245ca/butane 41.9/58.1  40.8   281                                        HFC-245ca/cyclopropane                                                                         12.1/87.9  106.9  737                                        HFC-245ca/isobutane                                                                            30.1/69.9  56.3   388                                        HFC-245ca/propane                                                                               8.8/91.2  139.0  958                                        HFC-245cb/HFC-272ea                                                                            96.5/3.5   68.2   470                                        HFC-245cb/HFC-281ea                                                                            87.7/12.3  70.5   486                                        HFC-245cb/HFC-281fa                                                                            93.4/6.6   68.8   474                                        HFC-245cb/butane 93.3/6.7   68.5   472                                        HFC-245cb/cyclopropane                                                                         40.8/59.2  110.7  763                                        HFC-245cb/DME    68.9/31.1  107.0  738                                        HFC-245cb/isobutane                                                                            80.2/19.8  75.1   518                                        HFC-245cb/propane                                                                              24.3/75.7  139.7  963                                        HFC-245cb/propylene                                                                            28.2/71.8  172.9  1192                                       HFC-245ea/HFC-272ca                                                                             8.8/91.2  35.0   241                                        HFC-245ea/HFC-356mff                                                                           12.0/88.0  15.5   107                                        HFC-245ea/HFC-356mmz                                                                            9.4/90.6  17.2   119                                        HFC-245ea/HFC-4310mee                                                                          34.4/65.6  3.50   24                                         HFC-245ea/butane 28.9/71.1  39.6   273                                        HFC-245ea/cyclopropane                                                                          8.6/91.4  106.4  734                                        HFC-245ea/isobutane                                                                            21.3/78.7  54.3   374                                        HFC-245ea/propane                                                                               5.9/94.1  138.6  956                                        HFC-245eb/HFC-263ca                                                                            26.3/73.7  18.4   127                                        HFC-245eb/HFC-263fb                                                                             6.3/93.7  54.4   375                                        HFC-245eb/HFC-356mff                                                                           45.1/54.9  20.0   138                                        HFC-245eb/HFC-356mmz                                                                           38.5/61.5  21.4   148                                        HFC-245eb/butane 43.5/56.5  43.5   300                                        HFC-245eb/cyclopropane                                                                         13.6/86.4  107.1  738                                        HFC-245eb/isobutane                                                                            33.5/66.5  57.4   396                                        HFC-245eb/propane                                                                               9.9/90.1  139.1  959                                        HFC-245fa/HFC-263ca                                                                            23.2/76.8  18.0   124                                        HFC-245fa/HFC-272ca                                                                            10.1/89.9  34.6   239                                        HFC-245fa/butane 48.6/51.4  40.9   282                                        HFC-245fa/cyclopropane                                                                          2.3/97.7  105.1  725                                        HFC-245fa/isobutane                                                                            33.7/66.3  53.9   372                                        ______________________________________                                    

A phase study shows the following compositions are azeotrope-like, allat 25° C.

    ______________________________________                                                               Vapor Press.                                           Composition No.        psia (kPa)                                             ______________________________________                                        HFC-245ca/HFC-263fb                                                                             1.0/99.0 54.0 372                                           HFC-245cb/HFC-245eb                                                                            99.5/0.5  67.4 465                                           HFC-245cb/HFC-254ca                                                                            98.6/1.4  67.5 465                                           HFC-245ea/HFC-272ea                                                                             5.6/94.4 20.8 143                                           HFC-245fa/HFC-272fb                                                                             3.5/96.5 26.5 183                                           ______________________________________                                    

EXAMPLE 2 Impact of Vapor Leakage on Vapor Pressure at 25° C.

A vessel is charged with an initial composition at 25° C., and theinitial vapor pressure of the composition is measured. The compositionis allowed to leak from the vessel, while the temperature is heldconstant at 25° C., until 50 weight percent of the initial compositionis removed, at which time the vapor pressure of the compositionremaining in the vessel is measured. The results are summarized below.

    ______________________________________                                                                             DEL-                                                    INITIAL    50% LEAK   TA %                                     WT % A/WT % B  PSIA    KPA    PSIA  KPA  P                                    ______________________________________                                        HFC-245ca/HFC-245eb                                                           75.0/25.0      14.1    97     14.1  97   0.0                                  90/10          14.2    98     14.2  98   0.0                                  99/1           14.2    98     14.2  98   0.0                                  50/50          14.5    100    14.4  99   0.7                                  30/70          15.3    105    15.1  104  1.3                                  10/90          16.3    112    16.2  112  0.6                                  1/99           16.9    117    16.8  116  0.6                                  HFC-245ca/HFC-263fb                                                           1.0/99.0       54.0    372    54.0  372  0.0                                  30/70          50.7    350    47.4  327  6.5                                  35/65          49.7    343    45.1  311  9.3                                  36/64          49.5    341    44.6  308  9.9                                  HFC-245ca/HFC-272ca                                                           17.2/82.8      35.8    247    35.8  247  0.0                                  1/99           34.7    239    34.6  239  0.3                                  50/50          34.0    234    31.6  218  7.1                                  55/45          33.4    230    30.1  208  9.9                                  HFC-245ca/HFC-272ea                                                           17.6/82.4      21.1    145    21.1  145  0.0                                  1/99           20.8    143    20.8  143  0.0                                  40/60          20.7    143    20.5  141  1.0                                  60/40          19.6    135    19.0  131  3.1                                  80/20          17.6    121    16.7  115  5.1                                  99/1           14.4    99     14.3  99   0.7                                  HFC-245ca/HFC-356mff                                                          28.0/72.0      16.9    117    16.9  117  0.0                                  15/85          16.7    115    16.6  114  0.6                                  1/99           15.1    104    14.8  102  2.0                                  60/40          16.2    112    16.0  110  1.2                                  80/20          15.3    105    15.1  104  1.3                                  99/1           14.2    98     14.2  98   0.0                                  HFC-245ca/HFC-356mmz                                                          21.6/78.4      18.5    128    18.5  128  0.0                                  10/90          18.2    125    18.0  124  1.1                                  1/99           17.0    117    16.7  115  1.8                                  60/40          17.1    118    16.6  114  2.9                                  80/20          15.7    108    15.3  105  2.5                                  99/1           14.3    99     14.2  98   0.7                                  HFC-245ca/butane                                                              41.9/58.1      40.8    281    40.8  281  0.0                                  20/80          39.9    275    38.3  264  4.0                                  10/90          38.5    265    36.2  250  6.0                                  1/99           35.7    246    35.3  243  1.1                                  60/40          40.4    279    39.8  274  1.5                                  73/27          39.7    274    35.8  247  9.8                                  74/26          39.6    273    35.0  241  11.6                                 HFC-245ca/cyclopropane                                                        12.1/87.9      106.9   737    106.9 737  0.0                                  1/99           105.5   727    105.2 725  0.3                                  40/60          105.3   726    102.7 708  2.5                                  55/45          103.2   712    93.4  644  9.5                                  56/44          102.7   708    92.3  636  10.1                                 HFC-245ca/isobutane                                                           30.1/69.9      56.3    388    56.3  388  0.0                                  15/85          55.9    385    54.1  373  3.2                                  1/99           51.4    354    50.5  348  1.8                                  50/50          56.0    386    55.2  381  1.4                                  65/35          55.0    379    49.7  343  9.6                                  66/34          54.9    379    48.8  336  11.1                                 HFC-245ca/propane                                                             8.8/91.2       139.0   958    139.0 958  0.0                                  1/99           138.2   953    138.0 951  0.1                                  40/60          136.3   940    133.3 919  2.2                                  50/50          134.8   929    128.0 883  5.0                                  57/43          133.3   919    120.9 834  9.3                                  58/42          133.0   917    119.4 823  10.2                                 HFC-245cb/HFC-245eb                                                           99.5/0.5       67.4    465    67.4  465  0.0                                  70/30          61.8    426    56.1  387  9.2                                  69/31          61.6    425    55.4  382  10.1                                 HFC-245cb/HFC-254ca                                                           98.6/1.4       67.5    465    67.5  465  0.0                                  99/1           67.5    465    67.5  465  0.0                                  75/25          63.0    434    57.5  396  8.7                                  74/26          62.8    433    56.8  392  9.6                                  HFC-245cb/HFC-272ea                                                           96.5/3.5       68.2    470    68.2  470  0.0                                  99/1           67.8    467    67.8  467  0.0                                  80/20          64.9    447    61.1  421  5.9                                  75/25          63.4    437    57.1  394  9.9                                  HFC-245cb/HFC-281ea                                                           87.7/12.3      70.5    486    70.5  486  0.0                                  99/1           68.1    470    67.9  468  0.3                                  50/50          63.7    439    59.7  412  6.3                                  40/60          60.8    419    56.1  387  7.7                                  30/70          57.6    397    52.9  365  8.2                                  20/80          54.3    374    50.4  347  7.2                                  1/99           47.5    328    47.3  326  0.4                                  HFC-245db/HFC-281fa                                                           93.4/6.6       68.8    474    68.8  474  0.0                                  99/1           67.9    468    67.8  467  0.1                                  60/40          61.2    422    55.5  383  9.3                                  59/41          60.8    419    54.9  379  9.7                                  58/42          60.5    417    54.4  375  10.1                                 HFC-245cb/butane                                                              93.3/6.7       68.5    472    68.5  472  0.0                                  99/1           67.7    467    67.7  467  0.0                                  70/30          64.5    445    61.6  425  4.5                                  60/40          62.0    427    56.2  387  9.4                                  59/41          61.7    425    55.6  383  9.9                                  HFC-245cb/cyclopropane                                                        40.8/59.2      110.7   763    110.7 763  0.0                                  20/80          109.4   754    108.7 749  0.6                                  1/99           105.3   726    105.2 725  0.1                                  70/30          106.6   735    103.4 713  3.0                                  85/15          97.0    669    88.8  612  8.5                                  90/10          90.6    625    81.6  563  9.9                                  91/9           89.1    614    80.1  552  10.1                                 HFC-245cb/DME                                                                 68.9/31.1      107.0   738    107.0 738  0.0                                  85/15          104.4   720    100.0 689  4.2                                  89/11          102.1   704    92.2  636  9.7                                  90/10          101.3   698    89.4  616  11.7                                 40/60          102.4   706    98.1  676  4.2                                  20/80          95.2    656    90.2  622  5.3                                  10/90          90.7    625    87.6  604  3.4                                  1/99           86.2    594    85.9  592  0.3                                  HFC-245cb/isobutane                                                           80.2/19.8      75.1    518    75.1  518  0.0                                  90/10          73.9    510    73.3  505  0.8                                  99/1           68.6    473    68.1  470  0.7                                  50/50          70.9    489    66.9  461  5.6                                  40/60          68.3    471    61.9  427  9.4                                  HFC-245cb/propane                                                             24.3/75.7      139.7   963    139.7 963  0.0                                  10/90          139.0   958    138.9 958  0.1                                  1/99           138.0   951    137.9 951  0.1                                  50/50          137.3   947    135.7 936  1.2                                  70/30          129.9   896    122.0 841  6.1                                  76/24          124.8   860    113.8 785  8.8                                  77/23          125.6   866    112.1 773  10.7                                 HFC-245cb/propylene                                                           28.2/71.8      172.9   1192   172.9 1192 0.0                                  10/90          170.6   1176   169.3 1167 0.8                                  1/99           166.6   1149   166.2 1146 0.2                                  60/40          167.0   1151   159.2 1098 4.7                                  69/31          161.5   1114   145.7 1005 9.8                                  70/30          160.6   1107   143.7 991  10.5                                 HFC-245ea/HFC-272ca                                                           8.8/91.2       35.0    241    35.0  241  0.0                                  1/99           34.6    239    34.6  239  0.0                                  40/60          33.4    230    31.3  216  6.3                                  45/55          32.9    227    29.8  205  9.4                                  46/54          32.8    226    29.5  203  10.1                                 HFC-245ea/HFC-272ea                                                           5.6/94.4       20.8    143    20.8  143  0.0                                  1/99           20.8    143    20.8  143  0.0                                  40/60          19.7    136    18.9  130  4.1                                  55/45          18.6    128    16.8  116  9.7                                  56/44          18.5    128    16.6  114  10.3                                 HFC-245ea/HFC-356mff                                                          12.0/88.0      15.5    107    15.5  107  0.0                                  1/99           14.9    103    14.8  102  0.7                                  40/60          14.5    100    13.6  94   6.2                                  54/46          13.4    92     12.1  83   9.7                                  55/45          13.3    92     11.9  82   10.5                                 HFC-245ea/HFC-356mmz                                                          9.4/90.6       17.2    119    17.2  119  0.0                                  1/99           16.8    116    16.7  115  0.6                                  40/60          15.8    109    14.5  100  8.2                                  45/55          15.3    105    13.8  95   9.8                                  46/54          15.2    105    13.6  94   10.5                                 HFC-245ea/HFC-4310mee                                                         34.4/65.6      3.50    24     3.50  24   0.0                                  15/85          3.81    26     3.70  26   2.9                                  1/99           4.32    30     4.30  30   0.5                                  50/50          3.77    26     3.58  25   5.0                                  56/44          4.05    28     3.66  25   9.6                                  57/43          410     28     3.68  25   10.2                                 HFC-245ea/butane                                                              28.9/71.1      39.6    273    39.6  273  0.0                                  10/90          39.1    270    36.0  248  7.9                                  1/99           36.2    250    35.2  243  2.8                                  60/40          39.2    270    37.3  257  4.8                                  65/35          38.9    268    35.2  243  9.5                                  66/34          38.9    268    34.6  239  11.1                                 HFC-245ea/cyclopropane                                                        8.6/91.4       106.4   734    106.4 734  0.0                                  1/99           105.5   727    105.2 725  0.3                                  40/60          105.0   724    102.2 705  2.7                                  54/46          103.2   712    93.5  645  9.4                                  55/45          103.0   710    92.5  638  10.2                                 HFC-245ea/isobutane                                                           21.3/78.7      54.3    374    54.3  374  0.0                                  10/90          54.0    372    52.7  363  2.4                                  1/99           51.4    354    50.5  348  1.8                                  40/60          54.1    373    53.7  370  0.7                                  62/38          53.2    367    47.9  330  10.0                                 HFC-245ea/propane                                                             5.9/94.1       138.6   956    138.6 956  0.0                                  1/99           138.1   952    138.0 951  0.1                                  40/60          136.2   939    133.4 920  2.1                                  57/43          133.9   923    122.5 845  8.5                                  58/42          133.6   921    119.7 825  10.4                                 HFC-245eb/HFC-263ca                                                           26.3/73.7      18.4    127    18.4  127  0.0                                  10/90          18.3    126    18.3  126  0.0                                  1/99           18.2    125    18.2  125  0.0                                  60/40          18.1    125    18.1  125  0.0                                  80/20          17.7    122    17.6  121  0.6                                  99/1           17.0    117    17.0  117  0.0                                  HFC-245eb/HFC-263fb                                                           6.3/93.7       54.4    375    54.4  375  0.0                                  1/99           54.1    373    54.1  373  0.0                                  40/60          50.9    351    46.8  323  8.1                                  43/57          50.3    347    45.3  312  9.9                                  HFC-245eb/HFC-356mff                                                          45.1/54.9      20.0    138    20.0  138  0.0                                  20/80          19.3    133    18.5  128  4.1                                  11/89          18.3    126    16.5  114  9.8                                  10/90          18.2    125    16.2  112  11.0                                 60/40          19.8    137    19.7  136  0.5                                  80/20          18.8    130    18.4  127  2.1                                  99/1           17.0    117    17.0  117  0.0                                  HFC-245eb/HFC-356mmz                                                          38.5/61.5      21.4    148    21.4  148  0.0                                  20/80          20.9    144    20.4  141  2.4                                  1/99           17.2    119    16.7  115  2.9                                  70/30          20.2    139    19.6  135  3.0                                  85/15          18.9    130    18.2  125  3.7                                  99/1           17.1    118    17.0  117  0.6                                  HFC-245eb/butane                                                              43.5/56.5      43.5    300    43.5  300  0.0                                  21/79          43.0    296    38.9  268  9.5                                  20/80          42.9    296    38.3  264  10.7                                 71/29          42.5    293    38.7  267  8.9                                  72/28          42.4    292    38.1  263  10.1                                 HFC-245eb/cyclopropane                                                        13.6/86.4      107.1   738    107.1 738  0.0                                  1/99           105.5   727    105.2 725  0.3                                  40/60          105.6   728    103.1 711  2.4                                  56/44          102.8   709    92.9  641  9.6                                  57/43          102.5   707    91.8  633  10.4                                 HFC-245eb/isobutane                                                           33.5/66.5      57.4    396    57.4  396  0.0                                  20/80          57.1    394    55.9  385  2.1                                  10/90          55.8    385    51.8  357  7.2                                  1/99           51.5    355    50.5  348  1.9                                  60/40          56.5    390    54.0  372  4.4                                  66/34          56.0    386    50.7  350  9.5                                  67/33          55.8    385    49.9  344  10.6                                 HFC-245eb/propane                                                             9.9/90.1       139.1   959    139.1 959  0.0                                  1/99           138.1   952    138.0 951  0.1                                  40/60          136.5   941    133.4 920  2.3                                  57/43          133.1   918    120.5 831  9.5                                  58/42          132.8   916    119.1 821  10.3                                 HFC-245fa/HFC-263ca                                                           23.2/76.8      18.0    124    18.0  124  0.0                                  10/90          18.1    125    18.1  125  0.0                                  1/99           18.2    125    18.2  125  0.0                                  40/60          18.2    125    18.2  125  0.0                                  60/40          18.8    130    18.6  128  1.1                                  80/20          19.9    137    19.7  136  1.0                                  99/1           21.3    147    21.3  147  0.0                                  HFC-245fa/HFC-272ca                                                           10.1/89.9      34.6    239    34.6  239  0.0                                  1/99           34.5    238    34.5  238  0.0                                  40/60          33.8    233    33.5  231  0.9                                  70/30          30.7    212    29.0  200  5.5                                  85/15          27.4    189    25.1  173  8.4                                  90/10          25.8    178    23.8  164  7.8                                  99/1           22.0    152    21.6  149  1.8                                  HFC-245fa/HFC-272fb                                                           3.5/96.5       26.5    183    26.5  183  0.0                                  1/99           26.5    183    26.5  183  0.0                                  40/60          26.0    179    26.0  179  0.0                                  70/30          24.7    170    24.5  169  0.8                                  85/15          23.5    162    23.1  159  1.7                                  99/1           21.6    149    21.6  149  0.0                                  HFC-245fa/butane                                                              48.6/51.4      40.9    282    40.9  282  0.0                                  30/70          40.4    279    39.6  273  2.0                                  10/90          37.8    261    36.3  250  4.0                                  1/99           35.5    245    35.3  243  0.6                                  70/30          40.1    276    38.6  266  3.7                                  78/22          38.9    268    35.1  242  9.8                                  79/21          38.7    267    34.5  238  10.9                                 HFC-245fa/cyclopropane                                                        2.3/97.7       105.1   725    105.1 725  0.0                                  1/99           105.1   725    105.1 725  0.0                                  40/60          101.2   698    98.0  676  3.2                                  56/44          97.2    670    88.0  607  9.5                                  57/43          96.8    667    87.0  600  10.1                                 HFC-245fa/isobutane                                                           33.7/66.3      53.9    372    53.9  372  0.0                                  20/80          53.5    369    53.1  366  0.7                                  10/90          52.5    362    51.8  357  1.3                                  1/99           50.7    350    50.6  349  0.2                                  60/40          52.6    363    50.8  350  3.4                                  70/30          51.1    352    46.1  318  9.8                                  71/29          50.9    351    45.4  313  10.8                                 ______________________________________                                    

The results of this Example show that these compositions are azeotropicor azeotrope-like because when 50 wt. % of an original composition isremoved, the vapor pressure of the remaining composition is within about10% of the vapor pressure of the original composition, at a temperatureof 25° C.

EXAMPLE 3 Impact of Vapor Leakage at 0° C.

A leak test is performed on compositions of HFC-245ca and HFC-272ca, atthe temperature of 0° C. The results are summarized below.

    ______________________________________                                                    INITIAL  50% LEAK   DELTA                                         WT % A/WT % B PSIA    KPA    PSIA  KPA  % P                                   ______________________________________                                        HFC-245ca/HFC-272ca                                                           15.2/84.8     15.4    106    15.4  106  0.0                                   1/99          15.0    103    15.0  103  0.0                                   40/60         15.0    103    14.4  99   4.0                                   52/48         14.4    99     13.0  90   9.7                                   53/47         14.4    99     12.8  88   11.1                                  ______________________________________                                    

These results show that compositions of HFC-245ca and HFC-272ca areazeotropic or azeotrope-like at different temperatures, but that theweight percents of the components vary as the temperature is changed.

EXAMPLE 4 Refrigerant Performance

The following table shows the performance of various refrigerants. Thedata are based on the following conditions.

Evaporator temperature 45.0° F. (7.2° C.)

Condenser temperature 130.0° F. (54.4° C.)

Subcooled 15.0° F. (a.3° C.)

Return gas 65.0° F. (18.3° C.)

Compressor efficiency is 75%.

The refrigeration capacity is based on a compressor with a fixeddisplacement of 3.5 cubic feet per minute and 75% volumetric efficiency.Capacity is intended to mean the change in enthalpy of the refrigerantin the evaporator per pound of refrigerant circulated, i.e. the heatremoved by the refrigerant in the evaporator per time. Coefficient ofperformance (COP) is intended to mean the ratio of the capacity tocompressor work. It is a measure of refrigerant energy efficiency.

    ______________________________________                                               Evap.     Cond.     Comp. Dis.   Capacity                              Refrig.                                                                              Press.    Press.    Temp.        BTU/                                  Comp.  Psia (kPa)                                                                              Psia (kPa)                                                                              °F. (°C.)                                                               COP  min (kw)                              ______________________________________                                        HFC-245ca/HFC-245eb                                                           1.0/99.0                                                                             8 55      43 296    157 69  3.72 46 0.8                                99.0/1.0                                                                             7 48      37 255    158 70  3.74 39 0.7                                HFC-245ca/HFC-263fb                                                           1.0/99.0                                                                             30 207    119 820   155 68  3.53 128 2.3                               99.0/1.0                                                                             7 48      37 255    158 70  3.76 40 0.7                                HFC-245ca/HFC-272ca                                                           1.0/99.0                                                                             19 131    78 538    161 72  3.70 89 1.6                                99.0/1.0                                                                             7 48      37 255    158 70  3.75 40 0.7                                HFC-245ca/HFC-272ea                                                           1.0/99.0                                                                             11 76     51 352    171 77  3.80 58 1.0                                99.0/1.0                                                                             7 48      37 255    158 70  3.75 39 0.7                                HFC-245ca/HFC-356mff                                                          1.0/99.0                                                                             7 48      38 262    138 59  3.54 38 0.7                                99.0/1.0                                                                             7 48      37 255    158 70  3.74 39 0.7                                HFC-245ca/HFC-356mmz                                                          1.0/99.0                                                                             8 55      42 290    137 58  3.53 42 0.7                                99.0/1.0                                                                             7 48      37 255    158 70  3.74 39 0.7                                HFC-245ca/butane                                                              1.0/99.0                                                                             20 138    81 558      155 68.3                                                                            3.66 91 1.6                                99.0/1.0                                                                             8 55      40 276      155 68.3                                                                            3.99 46 0.8                                HFC-245ca/cyclopropane                                                        1.0/99.0                                                                             62 427    214 1475  200 93  3.67 258 4.5                               99.0/1.0                                                                             8 55      40 276    157 69  3.93 46 0.8                                HFC-245ca/isobutane                                                           1.0/99.0                                                                             29 200    110 758   152 67  3.56 120 2.1                               99.0/1.0                                                                             7 48      38 262    158 70  3.77 41 0.7                                HFC-245ca/propane                                                             1.0/99.0                                                                             83 572    270 1862  167 75  3.31 280 4.9                               99.0/1.0                                                                             8 55      40 276    156 69  3.96 46 0.8                                HFC-245cb/HFC-245eb                                                           1.0/99.0                                                                             8 55      44 303    156 69  3.73 47 0.8                                99.5/0.5                                                                             36 248    136 938   139 59  3.31 135 2.4                               HFC-245cb/HFC-254ca                                                           1.0/99.0                                                                             7 48      36 248    161 72  3.79 39 0.7                                98.6/1.4                                                                             35 241    134 924   140 60  3.31 133 23                                HFC-245cb/HFC-272ea                                                           1.0/99.0                                                                             11 76     51 352    171 77  3.81 58 1.0                                99.0/1.0                                                                             36 248    136 938   139 59  3.32 135 2.4                               HFC-245cb/HFC-281ea                                                           1.0/99.0                                                                             27 186    105 724   168 76  3.69 121 2.1                               99.0/1.0                                                                             36 248    137 945   139 59  3.31 136 2.4                               HFC-245cb/HFC-281fa                                                           1.0/99.0                                                                             21 145    87 600    169 76  3.72 100 1.8                               99.0/1.0                                                                             36 248    137 945   139 59  3.31 136 2.4                               HFC-245cb/butane                                                              1.0/99.0                                                                             20 138    81 558    155 68  3.65 90 1.6                                99.0/1.0                                                                             36 248    136 938   139 59  3.31 135 2.4                               HFC-245cb/cyclopropane                                                        1.0/99.0                                                                             63 434    215 1482  200 93  3.67 259 4.6                               99.0/1.0                                                                             37 255    141 972   140 60  3.33 141 2.5                               HFC-245cb/DME                                                                 1.0/99.0                                                                             48 331    182 1255  193 89  3.67 214 3.8                               99.0/1.0                                                                             37 255    141 972   140 60  3.32 141 2.5                               HFC-245cb/isobutane                                                           1.0/99.0                                                                             29 200    110 758   152 67  3.56 121 2.1                               99.0/1.0                                                                             36 248    136 938   139 59  3.31 136 2.4                               HFC-245cb/propane                                                             1.0/99.0                                                                             84 579    271 1868  166 74  3.32 282 5.0                               99.0/1.0                                                                             37 255    140 965   140 60  3.32 140 2.5                               HFC-245cb/propylene                                                           1.0/99.0                                                                             104 717   331 2282  184 84  3.30 351 6.2                               99.0/1.0                                                                             38 262    142 979   140 60  3.35 143 2.5                               HFC-245ea/HFC-272ca                                                           1.0/99.0                                                                             19 131    78 538    161 72  3.70 88 1.5                                99.0/1.0                                                                             4 28      24 165    168 76  3.86 26 0.5                                HFC-245ea/HFC-272ea                                                           1.0/99.0                                                                             11 76     51 352    171 77  3.80 57 1.0                                99.0/1.0                                                                             4 28      24 165    168 76  3.83 25 0.4                                HFC-245ea/HFC-356mff                                                          1.0/99.0                                                                             7 48      38 262    138 59  3.54 38 0.7                                99.0/1.0                                                                             4 28      24 165    168 76  3.83 25 0.4                                HFC-245ea/HFC-356mmz                                                          1.0/99.0                                                                             8 55      42 290    137 58  3.53 42 0.7                                99.0/1.0                                                                             4 28      24 165    168 76  3.83 25 0.4                                HFC-245ea/HFC-4310mee                                                         1.0/99.0*                                                                            2 14      16 110    133 56  3.46 13 0.2                                99.0/1.0                                                                             4 28      23 159    167 75  3.82 25 0.4                                70° F. Return Gas                                                      HFC-245ea/butane                                                              1.0/99.0                                                                             19 131    80 552    155 68  3.66 89 1.6                                99.0/1.0                                                                             4 28      24 165    167 75  3.86 26 0.5                                HFC-245ea/cyclopropane                                                        1.0/99.0                                                                             61 421    213 1469  201 94  3.65 256 4.5                               99.0/1.0                                                                             5 34      27 186    165 74  4.14 31 0.5                                HFC-245ea/isobutane                                                           1.0/99.0                                                                             29 200    109 752   152 67  3.55 120 2.1                               99.0/1.0                                                                             4 28      25 172    167 75  3.92 27 0.5                                HFC-245ea/propane                                                             1.0/99.0                                                                             82 565    269 1855  166 74  3.31 279 4.9                               99.0/1.0                                                                             5 34      27 186    163 73  4.25 33 0.6                                HFC-245eb/HFC-263ca                                                           1.0/99.0                                                                             9 62      45 310    162 72  3.77 50 0.9                                99.0/1.0                                                                             8 55      43 296    157 69  3.72 46 0.8                                HFC-245eb/HFC-263fb                                                           1.0/99.0                                                                             30 207    199 1372  155 68  3.53 128 2.3                               99.0/1.0                                                                             9 62      44 303    157 69  3.72 47 0.8                                HFC-245eb/HFC-356mmf                                                          1.0/99.0                                                                             7 48      38 262    138 59  3.54 38 0.7                                99.0/1.0                                                                             8 55      43 296    156 69  3.72 46 0.8                                HFC-245eb/HFC-356mmz                                                          1.0/99.0                                                                             8 55      42 290    137 58  3.53 42 0.7                                99.0/1.0                                                                             8 55      43 296    156 69  3.71 46 0.8                                HFC-245eb/butane                                                              1.0/99.0                                                                             19 131    80 552    155 68  3.65 90 1.6                                99.0/1.0                                                                             9 62      44 303    157 69  3.72 47 0.8                                HFC-245eb/cyclopropane                                                        1.0/99.0                                                                             62 427    214 1475  200 93  3.66 258 4.5                               99.0/1.0                                                                             9 62      47 324    156 69  3.87 53 0.9                                HFC-245eb/isobutane                                                           1.0/99.0                                                                             29 200    110 758   152 67  3.56 120 2.1                               99.0/1.0                                                                             9 62      44 303    156 69  3.74 47 0.8                                HFC-245eb/propane                                                             1.0/99.0                                                                             83 572    270 1862  166 74  3.32 281 4.9                               99.0/1.0                                                                             10 69     47 324    155 68  3.88 53 0.9                                HFC-245fa/HFC-263ca                                                           1.0/99.0                                                                             9 62      45 310    162 72  3.77 50 0.9                                99.0/1.0                                                                             11 76     54 372    155 68  3.67 57 1.0                                HFC-245fa/HFC-272ca                                                           1.0/99.0                                                                             19 131    78 538    161 72  3.70 89 1.6                                99.0/1.0                                                                             11 76     54 372    155 68  3.67 58 1.0                                HFC-245fa/HFC-272fb                                                           1.0/99.0                                                                             14 97     63 434    169 76  3.76 72 1.3                                99.0/1.0                                                                             11 76     54 372    155 68  3.67 58 1.0                                HFC-245fa/butane                                                              1.0/99.0                                                                             19 131    80 552    155 68  3.66 90 1.6                                99.0/1.0                                                                             11 76     54 372    155 68  3.67 58 1.0                                HFC-245fa/cyclopropane                                                        1.0/99.0                                                                             62 427    214 1475  200 93  3.67 258 4.5                               99.0/1.0                                                                             12 83     58 400    155 68  3.79 64 1.1                                HFC-245fa/isobutane                                                           1.0/99.0                                                                             29 200    110 758   152 67  3.56 120 2.1                               99.0/1.0                                                                             11 76     55 379    155 68  3.68 59 1.0                                ______________________________________                                    

EXAMPLE 5

This Example is directed to measurements of the liquid/vapor equilibriumcurves for the mixtures in FIGS. 1-6 and 8-44.

Turning to FIG. 1, the upper curve represents the composition of theliquid, and the lower curve represents the composition of the vapor.

The data for the compositions of the liquid in FIG. 1 are obtained asfollows. A stainless steel cylinder is evacuated, and a weighed amountof HFC-245ca is added to the cylinder. The cylinder is cooled to reducethe vapor pressure of HFC-245ca, and then a weighed amount of HFC-245ebis added to the cylinder. The cylinder is agitated to mix the HFC-245caand HFC-245eb, and then the cylinder is placed in a constant temperaturebath until the temperature comes to equilibrium at 25° C., at which timethe vapor pressure of the HFC-245ca and HFC-245eb in the cylinder ismeasured. Additional samples of liquid are measured the same way, andthe results are plotted in FIG. 1.

The curve which shows the composition of the vapor is calculated usingan ideal gas equation of state.

Vapor/liquid equilibrium data are obtained in the same way for themixtures shown in FIGS. 2-6 and 8-44.

The data in FIGS. 2-6, 8-25, 27-38 and 40-44 show that at 25° C., thereare ranges of compositions that have vapor pressures as high as orhigher than the vapor pressures of the pure components of thecomposition at that same temperature. As stated earlier, the higher thanexpected pressures of these compositions may result in an unexpectedincrease in the refrigeration capacity and efficiency for thesecompositions versus the pure components of the compositions.

The data in FIGS. 1, 26 and 39 show that at 25° C., there are ranges ofcompositions that have vapor pressures below the vapor pressures of thepure components of the composition at that same temperature. Theseminimum boiling compositions are useful in refrigeration, and may showan improved efficiency when compared to the pure components of thecomposition.

EXAMPLE 6

This Example is directed to measurements of the liquid/vapor equilibriumcurve for mixtures of HFC-245ca and butane. The liquid/vapor equilibriumdata for these mixtures are shown in FIG. 7. The upper curve representsthe liquid composition, and the lower curve represents the vaporcomposition.

The procedure for measuring the composition of the liquid for mixturesof HFC-245ca and butane in FIG. 7 was as follows. A stainless steelcylinder was evacuated, and a weighed amount of HFC-245ca was added tothe cylinder. The cylinder was cooled to reduce the vapor pressure ofHFC-245ca, and then a weighed amount of butane was added to thecylinder. The cylinder was agitated to mix the HFC-245ca and butane, andthen the cylinder was placed in a constant temperature bath until thetemperature came to equilibrium at 20.0° C., at which time the vaporpressure of the content of the cylinder was measured. Samples of theliquid in the cylinder were taken and analyzed, and the results areplotted in FIG. 7 as asterisks, with a best fit curve having been drawnthrough the asterisks.

This procedure was repeated for various mixtures of HFC-245ca and butaneas indicated in FIG. 7.

The curve which shows the composition of the vapor is calculated usingan ideal gas equation of state.

The data in FIG. 7 show that at 20.0° C., there are ranges ofcompositions that have vapor pressures higher than the vapor pressuresof the pure components of the composition at that same temperature.

The novel compositions of this invention, including the azeotropic orazeotrope-like compositions, may be used to produce refrigeration bycondensing the compositions and thereafter evaporating the condensate inthe vicinity of a body to be cooled. The novel compositions may also beused to produce heat by condensing the refrigerant in the vicinity ofthe body to be heated and thereafter evaporating the refrigerant.

The compositions of the present inventions are useful as blowing agentsin the production of thermoset foams, which include polyurethane andphenolic foams, and thermoplastic foams, which include polystyrene orpolyolefin foams.

A polyurethane foam may be made by combining a composition of thepresent invention, which functions as a blowing agent, together with anisocyanate, a polyol, and appropriate catalysts or surfactants to form apoylurethane or polyisocyanurate reaction formulation. Water may beadded to the formulation raction to modify the foam polymer as well asto generate carbon dioxide as an in-situ blowing agent.

A phenolic foam may be produced by combining a phenolic resin or resole,acid catalysts, a blowing agent of the present invention and appropriatesurfactants to form a phenolic reaction formulation. The formulation maybe chosen such that either an open cell or closed cell phenolic foam isproduced.

Polystyrene or polyolefin foams may be made by extruing a molten mixureof a polymer, such as polystyrere, polyethylene or polypropylene), anucleating agent and a blowing agent of the present invention through anextrusion die that yields the desired foam product profile.

The novel compositions of this invention, including the azeotropic orazeotrope-like compositions, may be used as cleaning agents to clean,for example, electronic circuit boards. Electronic components aresoldered to circuit boards by coating the entire circuit side of theboard with flux and thereafter passing the flux-coated board overpreheaters and through molten solder. The flux cleans the conductivemetal parts and promotes solder fusion, but leave residues on thecircuit boards that must be removed with a cleaning agent. This isconventionally done by suspending a circuit board to be cleaned in aboiling sump which contains the azeotropic or azeotrope-likecomposition, then suspending the circuit board in a rinse sump, whichcontains the same azeotropic or azeotrope-like composition, and finally,for one minute in the solvent vapor above the boiling sump.

As a further example, the azeotropic mixtures of this invention can beused in cleaning processes such as described in U.S. Pat. No. 3,881,949,or as a buffing abrasive detergent.

It is desirable that the cleaning agents be azeotropic or azeotrope-likeso that they do not tend to fractionate upon boiling or evaporation.This behavior is desirable because if the cleaning agent were notazeotropic or azeotrope-like, the more volatile components of thecleaning agent would preferentially evaporate, and would result in acleaning agent with a changed composition that may become flammable andthat may have less-desirable solvency properties, such as lower rosinflux solvency and lower inertness toward the electrical components beingcleaned. The azeotropic character is also desirable in vapor degreasingoperations because the cleaning agent is generally redistilled andemployed for final rinse cleaning.

The novel compositions of this invention are also useful as fireextinguishing agents, heat transfer media, gaseous dielectrics, andpower cycle working fluids.

ADDITIONAL COMPOUNDS

Other components, such as aliphatic hydrocarbons having a boiling pointof -60 to +60° C., hydrofluorocarbonalkanes having a boiling point of-60° to +60° C., hydrofluoropropanes having a boiling point of between-60 to +60° C., hydrocarbon esters having a boiling point between -60 to+60° C., hydrochlorofluorocarbons having a boiling point between -60 to+60° C., hydrofluorocarbons having a boiling point of -60 to +60° C.,hydrochlorocarbons having a boiling point between -60 to +60° C.,chlorocarbons and perfluorinated compounds, can be added to theazeotropic or azeotrope-like compositions described above withoutsubstantially changing the properties thereof, including the constantboiling behavior, of the compositions.

Additives such as lubricants, corrosion inhibitors, surfactants,stabilizers, dyes and other appropriate materials may be added to thenovel compositions of the invention for a variety of purposes providesthey do not have an adverse influence on the composition for itsintended application. Preferred lubricants include esters having amolecular weight greater than 250.

We claim:
 1. An azeotropic or azeotrope-like composition consistingessentially of about 1-80 weight percent 1,1,2,2,3-pentafluoropropaneand about 20-99 weight percent 1,1,1,4,4,4-hexafluorobutane wherein saidcomposition has a vapor pressure of 15.1 to about 17 psia when thetemperature is adjusted to 25° C.; about 1-60 weight percent1,1,2,2,3-pentafluoropropane and about 40-99 weight percent (CF₃)₂ CHCH₃wherein said composition has a vapor pressure of 17 to about 18.5 psiawhen the temperature is adjusted to 25° C.; about 1-40 weight percent1,1,2,3,3-pentafluoropropane and about 60-99 weight percent1,1,1,4,4,4-hexafluorobutane wherein said composition has a vaporpressure of about 15 psia when the temperature is adjusted to 25° C.;about 1-10 weight percent 1,1,2,3,3-pentafluoropropane and about 90-99weight percent (CF₃)₂ CHCH₃ wherein said composition has a vaporpressure of about 17 psia when the temperature is adjusted to 25° C.;11-99 weight percent 1,1,1,2,3-pentafluoropropane and 1-89 weightpercent 1,1,1,4,4,4-hexafluorobutane wherein said composition has avapor pressure of 17 to about 20 psia when the temperature has beenadjusted to 25° C.; or 1-99 weight percent 1,1,1,2,3-pentafluoropropaneand 1-99 weight percent (CF₃)₂ CHCH₃ wherein said composition has avapor pressure of 17.1 to about 21.4 psia when the temperature has beenadjusted to 25° C.
 2. An azeotropic or azeotrope-like compositionconsisting essentially of about 1-80 weight percent1,1,2,2,3-pentafluoropropane and about 20-99 weight percent1,1,1,4,4,4-hexafluorobutane; about 1-60 weight percent 1,1,2,2,3-pentafluoropropane and about 40-99 weight percent (CF₃)₂ CHCH₃ ; about1- less than 40 weight percent 1,1,2,3,3-pentafluoropropane and greaterthan 60 to about 99 weight percent 1,1,1,4,4,-hexafluorobutane; about1-10 weight percent 1,1,2,3,3-pentafluoropropane and about 90-99 weightpercent (CF₃)₂ CHCH₃ ; 11-99 weight percent 1,1,1,2,3-pentafluoropropaneand 1-89 weight percent 1,1,1,4,4,4-hexafluorobutane; or 1-99 weightpercent 1,1,1,2,3-pentafluoropropane and 1-99 weight percent (CF₃)₂CHCH₃, wherein at 25° C. said composition has a vapor pressure that ishigher than the vapor pressure of the individual components at 25° C. 3.A process for producing refrigeration comprising condensing acomposition of claims 1 or 2 and thereafter evaporating said compositionin the vicinity of a body to be cooled.
 4. A process for producing heatcomprising condensing a composition of claims 1 or 2 in the vicinity ofa body to be heated, and thereafter evaporating said composition.